CN102177118A - Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride - Google Patents
Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride Download PDFInfo
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- CN102177118A CN102177118A CN2009801401143A CN200980140114A CN102177118A CN 102177118 A CN102177118 A CN 102177118A CN 2009801401143 A CN2009801401143 A CN 2009801401143A CN 200980140114 A CN200980140114 A CN 200980140114A CN 102177118 A CN102177118 A CN 102177118A
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- Prior art keywords
- chloro
- methyl
- acetate
- hfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 192
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 87
- JXLLSNNXICBZIS-UHFFFAOYSA-N (2-chloro-2,3,3,3-tetrafluoropropyl) acetate Chemical compound CC(=O)OCC(F)(Cl)C(F)(F)F JXLLSNNXICBZIS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- ZGDAIZKZNKWBTM-UHFFFAOYSA-N 2-chloro-2,3,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(Cl)C(F)(F)F ZGDAIZKZNKWBTM-UHFFFAOYSA-N 0.000 title abstract description 3
- YZNCFBREKILROT-UHFFFAOYSA-N (2-chloro-2,3,3,3-tetrafluoropropyl) hypochlorite;zinc Chemical compound [Zn].FC(F)(F)C(F)(Cl)COCl YZNCFBREKILROT-UHFFFAOYSA-N 0.000 title 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 160
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 131
- 150000001875 compounds Chemical class 0.000 claims abstract description 127
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 claims abstract description 83
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 claims abstract description 64
- -1 CF3CHFCI) Chemical compound 0.000 claims abstract description 59
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 49
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 41
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 35
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 21
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 17
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims abstract description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims abstract description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims abstract description 7
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims abstract description 7
- MFOQKYXGXHZFDL-UHFFFAOYSA-N 3,4,4,4-tetrafluorobutan-2-one Chemical compound CC(=O)C(F)C(F)(F)F MFOQKYXGXHZFDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 claims abstract description 5
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical compound FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002904 solvent Substances 0.000 claims description 89
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 34
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 20
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 16
- 235000005074 zinc chloride Nutrition 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 7
- FHNBVEYDTSGFGE-UHFFFAOYSA-N 1-fluorobutan-2-one Chemical compound CCC(=O)CF FHNBVEYDTSGFGE-UHFFFAOYSA-N 0.000 claims description 6
- JVTSHOJDBRTPHD-UHFFFAOYSA-N 2,2,2-trifluoroacetaldehyde Chemical compound FC(F)(F)C=O JVTSHOJDBRTPHD-UHFFFAOYSA-N 0.000 claims description 6
- 229960003132 halothane Drugs 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 5
- MRQDALCRZBHBEM-UHFFFAOYSA-N 3-chloro-3,4,4,4-tetrafluorobutan-2-one Chemical compound CC(=O)C(F)(Cl)C(F)(F)F MRQDALCRZBHBEM-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 4
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- ANLMVXSIPASBFL-UHFFFAOYSA-N Streptamin D Natural products NC1C(O)C(N)C(O)C(O)C1O ANLMVXSIPASBFL-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- ANLMVXSIPASBFL-FAEUDGQSSA-N streptamine Chemical compound N[C@H]1[C@H](O)[C@@H](N)[C@H](O)[C@@H](O)[C@@H]1O ANLMVXSIPASBFL-FAEUDGQSSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011701 zinc Substances 0.000 abstract description 21
- 229910052725 zinc Inorganic materials 0.000 abstract description 17
- 238000004378 air conditioning Methods 0.000 abstract description 10
- 238000005057 refrigeration Methods 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 abstract 1
- JQEQBVHLTKCNTI-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropyl acetate Chemical compound CC(=O)OCC(F)C(F)(F)F JQEQBVHLTKCNTI-UHFFFAOYSA-N 0.000 abstract 1
- DASQIKOOFDJYKA-UHFFFAOYSA-N CCIF Chemical compound CCIF DASQIKOOFDJYKA-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 67
- 239000011541 reaction mixture Substances 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 239000007791 liquid phase Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229930040373 Paraformaldehyde Natural products 0.000 description 16
- 239000012535 impurity Substances 0.000 description 15
- 229920002866 paraformaldehyde Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 11
- 239000007810 chemical reaction solvent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006298 dechlorination reaction Methods 0.000 description 8
- 230000010354 integration Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000005906 dihydroxylation reaction Methods 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000008246 gaseous mixture Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 150000005828 hydrofluoroalkanes Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- OXQOBQJCDNLAPO-UHFFFAOYSA-N dimethylpyrazine Natural products CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BGJSXRVXTHVRSN-VMIGTVKRSA-N 1,3,5-trioxane Chemical group [13CH2]1O[13CH2]O[13CH2]O1 BGJSXRVXTHVRSN-VMIGTVKRSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QHNXEVRKFKHMRL-UHFFFAOYSA-N dimethylazanium;acetate Chemical compound CNC.CC(O)=O QHNXEVRKFKHMRL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Compositions comprising CF3CCIFCH2OH, CF3CCIFCH2OZnCI, and CF3CCIFCH2OC(=O)CH3 are useful in processes to make HFO- 1234yf. Compositions comprising HFO-1234yf may comprise at least one additional compound selected from the group consisting of CFC-114a (2- dichloro-1,1,1,2-tetrafluoroethane, CCI2FCF3), HCFC-124 (2-chloro- 1,1,1,2-tetrafluoroethane, CF3CHFCI), HFC-143a (1,1,1 -thfluoroethane, CF3CH3), CFO-1113 (2-chloro-1,1,2-trifluoroethene, CCIF=CF2), HFO- 1123 (1,1,2-trifluoroethene, CHF=CF2), HFO-1132a (1,1 -difluoroethene, CH2=CF2), TFE (tetrafluoroethene, CF2=CF2), HCFO-1122 (2-chloro- 1,1 - difluoroethene, CHCI=CF2), 3,4,4,4-tetrafluoro-2-butanone (CH3C(=O)CHFCF3), acetyl fluoride (CH3C(=O)F), 2-chloro-2,3,3,3- tetrafluoropropanol (CF3CCIFCH2OH), 2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF3CCIFCH2OC(=O)CH3), Zinc (2-chloro-2,3,3,3- tetrafluoropropoxy); chloride (CF3CCIFCH2OZnCI2-chloro-2,3,3,3- tetrafluoropropoxy methyl acetate (CF3CFCICH2OCH2OC(=O)CH3), 1,3- bisthfluoromethyl-1,3-difluorocyclobutane (C6H4F8), 2,3,3,3- tetrafluoropropyl acetate (CF3CHFCH2OC(=O)CH3), dimethylformamide (DMF, HCON(CH3)2), pyridine (C5H5N), ethyl acetate, (CHCIFCF3), acetic acid (CH3C(=O)OH), diethyl ether (CH3CH2OCH2CH3), acetic anhydride (CH3C(=O)OC(=O)CH3), methyl acetate (CH3C(=O)OCH3), dimethylacetamide (CH3C(=O)N(CH3)2), methanol (CH3OH), ethanol CH3CH2OH), methyl formate (HC(=O)OCH3), pyrazine, pyrimidine, N- methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide, tetrahydrofuran, 1,4-dioxane, N-methyl pyrrolidinone, dimethyl sulfoxide, acetonitrile, benzonithle, and mixtures thereof. Compositions comprising HFO-1234yf are useful, among other uses, as heat transfer compositions for use in refrigeration, air-conditioning and heat pump systems.
Description
The cross reference of related application
Present patent application requires the benefit of priority of the U.S. Provisional Application 61/104,334 of submission on October 10th, 2008.
Background of invention
1. open field
The disclosure of invention relates to compositions field, described composition can be used as swelling agent, gaseous dielectric, fire-fighting medium and the fireproofing agent of heat transfer composition, aerosol propellants, whipping agent, bubbling agent, solvent, sanitising agent, carrier fluid, substituted type siccative, polishing abrasive, polymerization reaction medium, polyolefine and urethane, and it is liquid state or gaseous form.Specifically, the disclosure of invention relates to the composition that can be used as heat transfer composition, such as 2,3,3, and 3-tetrafluoeopropene (HFO-1234yf or 1234yf).In addition, the disclosure of invention also relates to and comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol, acetate 2-chloro-2,3,3, the composition of 3-tetrafluoro propyl ester or (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride.
These additive compositions can be used for preparing in the method for HFO-1234yf.
2. background technology
The environment new regulation cause to can be used for freezing, the needs of novel compositions in air-conditioning and the thermal pump equipment.Low global warming potential composition especially receives publicity.
Summary of the invention
The applicant has found that some additional compound is to exist on a small quantity when preparing this type of novel low global warming potential compound such as HFO-1234yf.
Therefore, according to the present invention, provide the composition that comprises HFO-1234yf and at least a additional compound in one embodiment, described additional compound is selected from CFC-114a (2-two chloro-1,1,1,2-Tetrafluoroethane, CCl
2FCF
3), HCFC-124 (2-chloro-1,1,1,2-Tetrafluoroethane, CF
3CHFCl), HFC-143a (1,1,1-Halothane, CF
3CH
3), CFO-1113 (2-chloro-1,1,2-trifluoro-ethylene, CClF=CF
2), HFO-1123 (1,1,2-trifluoro-ethylene, CHF=CF
2), HFO-1132a (vinylidene fluoride, CH
2=CF
2), TFE (tetrafluoroethylene, CF
2=CF
2), HCFO-1122 (2-chloro-vinylidene fluoride, CHCl=CF
2), 3,4,4,4-tetrafluoro-2-butanone (CH
3C (=O) CHFCF
3), acetylfluoride (CH
3C (=O) F), 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl), acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters (CF
3CFClCH
2OCH
2OC (=O) CH
3), 1,3-bis trifluoromethyl-1,3-difluoro tetramethylene (C
6H
4F
8), acetate 2,3,3,3-tetrafluoro propyl ester (CF
3CHFCH
2OC (=O) CH
3), dimethyl formamide (DMF, HCON (CH
3)
2), pyridine (C
5H
5N), ethyl acetate, (CHClFCF
3), acetate (CH
3C (=O) OH), ether (CH
3CH
2OCH
2CH
3), diacetyl oxide (CH
3C (=O) OC (=O) CH
3), methyl acetate (CH
3C (=O) OCH
3), N,N-DIMETHYLACETAMIDE (CH
3C (=O) N (CH
3)
2), methyl alcohol (CH
3OH), ethanol (CH
3CH
2OH), methyl-formiate (HC (=O) OCH
3), pyrazine, pyrimidine, N-crassitude, N-methyl piperidine, hexamethyl-phosphoramide, tetrahydrofuran (THF), 1,4-dioxane, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), acetonitrile, benzonitrile and their mixture, their mixture is meant the mixture of listed any above-mentioned additional compound in this section.
In another embodiment, provide to comprise 2-chloro-3,3 3-trifluoropropanol (CF
3CClFCH
2OH), the composition of at least a solvent and optional at least a additional compound.
In another embodiment, provide to comprise acetate 2-chloro-2,3,3 3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), the composition of at least a solvent and optional at least a additional compound.
In another embodiment, provide and comprised (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl), the composition of at least a solvent and optional at least a additional compound.
The accompanying drawing summary
Fig. 1 illustrates the synoptic diagram that is used for being prepared by CFC-114a the differential responses of HFO-1234yf.
Detailed Description Of The Invention
Composition
(or be 114a or CF by CFC-114a3CFCl
2) preparation 2,3,3,3-tetrafluoeopropene (HFO-1234yf, CF3CF＝CH
2) method be shown among Fig. 1. As seen from Figure 1, CF3CClFCH
2OH、CF
3CClFCH
2OC(＝O)CH
3And CF3CClFCH
2OZnCl is the midbody compound that may form in the method.
With reference to Fig. 1, in one embodiment, process by zinc powder and paraformaldehyde with activation, CFC-114a can react and generate CF3CFClCH
2OH. This reaction can in the presence of solvent, be carried out in liquid phase. CF3CFClCH
2OH can form CF with carboxylic acid anhydrides (for example acetic anhydride) and reactive metal (for example zinc) reaction3CClFCH
2OC(＝O)CH
3, it can further react with reactive metal such as zinc in solvent and generate HFO-1234yf. In a particular, described solvent can be mixed solvent, such as DMF (dimethyl formamide) and pyridine. Yet should be pointed out that to the invention is not restricted to use these specific solvents, and multi-solvents such as listed those hereinafter can be used among the present invention.
Alternatively, in another embodiment, as shown in Figure 1, CFC-114a can generate CF with reactive metal and aldehyde reaction3CFClCH
2OZnCl. This reaction also can in the presence of solvent, be carried out in liquid phase. Equally, in a particular, described solvent can be mixed solvent, such as DMF (dimethyl formamide) and pyridine, should be pointed out that multi-solvents such as listed those hereinafter can be used among the present invention. CF3CFClCH
2OZnCl can further react with carboxylic acid anhydrides (for example acetic anhydride) and reactive metal (for example zinc) and form CF3CClFCH
2OC(＝O)CH
3, it can further react with reactive metal such as zinc in solvent and generate HFO-1234yf. In another embodiment, all above-mentioned reactions all can the branch multistep be carried out in single reaction vessel, wherein do not have midbody compound and are separated. This illustrates with the single arrow from CFC-114a to HFO-1234yf in Fig. 1.
2,3,3,3-tetrafluoeopropene (HFO-1234yf, CF3CF＝CH
2), 2-chloro-2,3,3,3-tetrafluoropropanol (CF3CClFCH
2OH), acetic acid 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF3CClFCH
2OC(＝O)CH
3) and (2-chloro-2,3,3,3-tetrafluoro propoxyl group) zinc chloride (CF3CClFCH
2OZnCl) can as described hereinly make.
In one embodiment, composition of the present invention comprises HFO-1234yf and at least a additional compound, and described additional compound is selected from the CFC-114a shown in Fig. 1 (2-two chloro-1,1,1,2-Tetrafluoroethane, CCl
2FCF
3), HCFC-124 (2-chloro-1,1,1,2-Tetrafluoroethane, CF
3CHFCl), HFC-143a (1,1,1-Halothane, CF
3CH
3), CFO-1113 (2-chloro-1,1,2-trifluoro-ethylene, CClF=CF
2), HFO-1123 (1,1,2-trifluoro-ethylene, CHF=CF
2), HFO-1132a (vinylidene fluoride, CH
2=CF
2), TFE (tetrafluoroethylene, CF
2=CF
2), HCFO-1122 (2-chloro-vinylidene fluoride, CHCl=CF
2), 3,4,4,4-tetrafluoro-2-butanone (CH
3C (=O) CHFCF
3), acetylfluoride (CH
32-chloro-2,3,3 shown in C (=O) F), Fig. 1,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), the acetate 2-chloro-2,3,3 shown in Fig. 1,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), (2-chloro-2,3,3, the 3-tetrafluoro propoxy-) zinc chloride (CF shown in Fig. 1
3CClFCH
2OZnCl), acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters (CF
3CFClCH
2OCH
2OC (=O) CH
3), 1,3-bis trifluoromethyl-1,3-difluoro tetramethylene (C
6H
4F
8), acetate 2,3,3,3-tetrafluoro propyl ester (CF
3CHFCH
2OC (=O) CH
3), dimethyl formamide (DMF, HCON (CH
3)
2), pyridine (C
5H
5N), ethyl acetate, (CHClFCF
3), acetate (CH
3C (=O) OH), ether (CH
3CH
2OCH
2CH
3), diacetyl oxide (CH
3C (=O) OC (=O) CH
3), methyl acetate (CH
3C (=O) OCH
3), N,N-DIMETHYLACETAMIDE (CH
3C (=O) N (CH
3)
2), methyl alcohol (CH
3OH), ethanol (CH3CH2OH), methyl-formiate (HC (=O) OCH
3), pyrazine, pyrimidine, N-crassitude, N-methyl piperidine, hexamethyl-phosphoramide, tetrahydrofuran (THF), 1,4-dioxane, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), acetonitrile, benzonitrile and their mixture, their mixture is meant the mixture of listed any above-mentioned additional compound in this section.Any composition in described this embodiment of this section is called as composition A hereinafter.These compositions are vapor phase or liquid phase compositions.
Fig. 1 is the representative diagram that is used to prepare the method for the present composition, and all listed additional compounds all are not shown among Fig. 1 in the epimere, should understand composition of the present invention and comprise all these additional compounds.The listed herein potential additional compound that is contained in the composition that comprises HFO-1234yf can be present in raw material or the solvent, and perhaps these additional compounds can be to be present in the reaction product that this type of additional compound in the raw material generates under the reaction conditions of preparation HFO-1234yf.
Reactive chemistry shown in described herein and Fig. 1 makes and does not comprise the HFO-1234yf that can detect HFO-1234ze (1,3,3, the 3-tetrafluoeopropene), and promptly it " is substantially free of " HFO-1234ze." being substantially free of " content that is meant HFO-1234ze is substantially zero.Detect the ability whether any component exist and depend on used analytical procedure and various other factors.In one embodiment, be substantially free of HFO-1234ze and be meant that described composition comprises by weight the HFO-1234ze less than 10 parts each 1,000,000 parts (ppm).In another embodiment, be substantially free of HFO-1234ze and be meant that described composition comprises by weight the HFO-1234ze less than 5ppm.In another embodiment, be substantially free of HFO-1234ze and be meant that described composition comprises by weight the HFO-1234ze less than 1ppm.
In one embodiment, the total amount of additional compound in comprising the composition vapor phase of HFO-1234yf greater than 0 weight % to the scope of about 30 weight %.In another embodiment, the total amount of additional compound greater than 0 weight % to about 20 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 10 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 5 weight % scopes.
In one embodiment, the total amount of additional compound in comprising the composition of HFO-1234yf greater than 0 weight % to the scope less than 1 weight %.
In some embodiments, some precursor compound of HFO-1234yf comprises impurity, and described impurity shows as the additional compound in the HFO-1234yf composition.In other embodiments, additional compound generates via the reaction of these precursor impurity.In other embodiments, the reaction conditions that makes HFO-1234yf also produces by product, described by product shows as the additional compound in the HFO-1234yf composition subsequently, this means according to the actual conditions that makes HFO-1234yf, can generate additional compound by alternative reaction path.
In another particular, composition of the present invention comprises HFO-1234yf and following additional compound: tetrafluoroethylene, vinylidene fluoride, trifluoro-ethylene and 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124).Representative impurity level in this embodiment is the 1234yf of about 80 weight %, the HCFC-124 of about 10 weight %, and surplus is tetrafluoroethylene, vinylidene fluoride, trifluoro-ethylene.
In another particular, composition of the present invention comprises HFO-1234yf and following additional compound: 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), diacetyl oxide, methyl acetate, DMF and pyridine.In this embodiment, the 1234yf greater than 90 weight % is arranged, the pyridine of about 2 weight % and about 1 weight % or all the other additional compounds still less.
In another particular, composition of the present invention comprises HFO-1234yf and following additional compound: tetrafluoroethylene (TFE), HFO-1123,1,1,1-Halothane (HFC-143a), CFO-1113, HCFC-124, CFC-114a, 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene, methyl-formiate, acetate and acetate 2,3,3,3-tetrafluoro propyl ester.In this embodiment, the exemplary impurity amount is about 10 weight % or HFO-1123 still less, HCFC-124 and 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene; And less than the resistates of about 1 weight %.
In another particular, composition of the present invention comprises HFO-1234yf and following additional compound: HFO-1123, water, CFO-1113,1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene, methyl-formiate and methyl acetate.In this embodiment, the exemplary impurity amount is about 1 weight % or HFO-1123 still less, water, CFO-1113,1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene, methyl-formiate and methyl acetate.
In another embodiment, the disclosure of invention provides and has comprised 1) 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), or 2) CF
3CClFCH
2OC (=O) CH
3Or 3) CF
3CClFCH
2OZnCl, and all comprise the composition of at least a solvent under every kind of situation.Comprise 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) and the composition of at least a solvent should be called as composition B hereinafter.Comprise acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3) and the composition of at least a solvent will be called as composition C hereinafter.Comprise (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) and the composition of at least a solvent will be called as composition D hereinafter.
In one embodiment, additional compound is comprising CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3Or CF
3CClFCH
2Total amount in the composition of OZnCl and at least a solvent by total composition greater than 0 weight % to about 50 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 30 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 10 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 5 weight % scopes.In another embodiment, the total amount of additional compound greater than 0 weight % to about 1 weight % scope.
In some embodiments, CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3Or CF
3CClFCH
2Some precursor compound of OZnCl comprises impurity, and described impurity is present in CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3Or CF
3CClFCH
2Among the OZnCl.In other embodiments, additional compound generates via the reaction of these precursor impurity.In other embodiments, make CF
3CClFCH2OH, CF
3CClFCH
2OC (=O) CH
3Or CF
3CClFCH
2The reaction conditions of OZnCl also generates by product, this means according to making CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3Or CF
3CClFCH
2The actual conditions of OZnCl can generate additional compound by alternative reaction path.With regard to these products that made by methods described herein, some other compound of being introduced by the solvent that is used for implementing chemical reaction can be present in described composition, perhaps can react generation and can be present in other compound in the described composition equally.
In one embodiment, described solvent is selected from pyridine, pyrazine or pyrimidine, alkyl nitrile and fragrant nitrile, hexamethyl-phosphoramide and their mixture of alkyl straight streptamine or cyclammonium, dialkyl group straight chain amine or cyclammonium and trialkyl straight chain amine or cyclammonium, N-crassitude, N-methyl piperidine, sulfoxide, ether, pyridine or alkyl replacement.In another embodiment, described solvent is selected from trialkylamine, N-crassitude, N-methyl piperidine, pyridine, pyridine, dimethyl formamide, pyrazine or the pyrimidine of alkyl replacement and their mixture.In another embodiment, described reaction solvent is selected from dimethyl formamide, tetrahydrofuran (THF), pyridine, N,N-DIMETHYLACETAMIDE, 1,4-dioxane, N-Methyl pyrrolidone, ether and their mixture.In another embodiment, described solvent is the pyridine that pyridine or alkyl replace, or their mixture.In another embodiment, described solvent is selected from alcohol, ester and their mixture.In another embodiment, described solvent is selected from methyl alcohol, ethanol, methyl-formiate, methyl-sulphoxide, acetonitrile, benzonitrile and their mixture, or the mixture of these and above-mentioned any other solvent.
In one embodiment, comprise CF
3CClFCH
2OH, CF
3CClFCH
2OZnCl or CF
3CClFCH
2OC (=O) CH
3In the solvent total amount that exists in any composition will change according to various factors.If sufficient amount of solvent is not provided, then reactant and/or product compound will not exist in solution entirely.In addition, if use too much solvent, then speed of reaction is with slack-off.In one embodiment, the content of described solvent be described composition at least about 90 weight %.In another embodiment, described solvent will be present in the described composition with at least 50 weight % of described composition.In another embodiment, described solvent will being present in the described composition at least about 30 weight % with described composition.In another embodiment, the content of described solvent is at least about 20 weight %.
In another embodiment, comprise CF
3CClFCH
2The composition of OH and at least a solvent also can comprise at least a additional compound, and described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, N,N-DIMETHYLACETAMIDE, methyl alcohol, methyl acetate, methyl-formiate, dimethyl formamide, pyridine, ethyl acetate, acetate, ether, CF
3CClFCH
2OZnCl, CF
3CClFCH
2OC (=O) CH
3, acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters and their mixture (meaning the mixture of listed any above-mentioned additional compound in this section).Should be pointed out that all listed compounds all are not shown among Fig. 1 herein, because Fig. 1 is intended to the representative diagram for the method for preparing the present composition.It is believed that these compounds show as impurities in raw materials, the impurity in the solvent perhaps is being used to make CF
3CClFCH
2The reaction conditions of OH reacts any in these dopant type that generate other compound down.Composition in described this embodiment of this section is called as composition B (1) hereinafter.
In a particular, described composition comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2And comprise HCFC-124 and methyl alcohol OH) and at least a solvent of forming by dimethyl formamide, as additional compound.In this embodiment, the content of solvent DMF is about 80 weight % or higher.HCFC-124 is about 8 weight % or still less, and methyl alcohol can be less than about 1 weight %.
In another particular, described composition comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) and at least a solvent of being made of pyridine, and comprise 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), methyl-formiate, trifluorochloroethylene (CFO-1113), trifluoro-ethylene (HFO-1123) and methyl alcohol are as additional compound.In this embodiment, the content of described pyridine solvent is about 80 weight % or more, and the content of HCFC-124 is about 3 weight % or still less, and other additional compound is about 1 weight % or still less.
In another particular, described composition comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) and at least a solvent of being made of N,N-DIMETHYLACETAMIDE, and comprise 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), methyl-formiate, trifluorochloroethylene (CFO-1113) and trifluoro-ethylene (HFO-1123) and methyl alcohol are as additional compound.The additional compound typical content of this embodiment is HCFC-124 and the CFO-1113 of each about 2 weight % to 3 weight %, and about 1 weight % or all the other lower compounds.
In another embodiment, comprise CF
3CClFCH
2OC (=O) CH
3Also can comprise at least a additional compound with the composition of at least a solvent, described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methyl alcohol, methyl acetate, methyl-formiate, N,N-DIMETHYLACETAMIDE, dimethyl formamide, pyridine, ethyl acetate, acetate, ether, diacetyl oxide, formaldehyde, 3-chloro-3,4,4,4-three fluoro-2-butanone, acetate 2,3,3,3-tetrafluoro propyl ester, CF
3CClFCH
2OCH (=O), acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters, CF
3CClFCH
2OH, CF
3CClFCH
2OZnCl and their mixture (meaning the mixture of listed any above-mentioned additional compound in this section).The described composition of the present invention of this section is called as composition C (1) hereinafter.Noticing equally, is not that all compounds of herein listing all are shown among Fig. 1.It is believed that these compounds are rendered as the impurity in impurities in raw materials, the solvent or are being used to prepare CF
3CClFCH
2OC (=O) CH
3Reaction conditions down reaction form in these type dopant of other compound any.
In a particular, composition wherein of the present invention comprises acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), at least a solvent and the additional compound of forming by ether, and described additional compound comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), ethyl acetate and acetate.The additional compound typical content of this embodiment is the acetate of about 17 weight %, the ethyl acetate of about 3 weight % and less than the 2-chloro-2,3 of about 1 weight %, 3, the 3-C3-Fluoroalcohol, described amount is all with respect to the acetate 2-chloro-2 in the described composition, 3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3) amount.
In another particular, composition wherein of the present invention comprises acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), at least a be the solvent and the additional compound of DMF and pyridine, described additional compound comprises formic acid 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OCH (=O)), 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), diacetyl oxide and acetate.In this embodiment, described solvent is the mixture of DMF and pyridine.The representativeness amount that is used for the additional compound of this embodiment is about 3 weight % or all lower additional compounds.
In a particular, composition wherein of the present invention comprises acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), at least a be the solvent and the additional compound of DMF and pyridine, described additional compound comprises TFE, HCFC-124,3-chloro-3,4,4,4-three fluoro-2-butanone (CF
3CClFCH
2C (=O) CH
3), ethyl-methyl ether and methyl acetate, it is liquid phase.In this embodiment, described solvent is the mixture of DMF and pyridine.The representativeness amount that is used for the additional compound of this embodiment is the acetate 2-chloro-2,3,3 of about 85 weight %, 3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), the 2-chloro-1,1,1 of about 6 weight %, the 3-chloro-3,4,4 of 2-Tetrafluoroethane (HCFC-124), about 2.5 weight %, 4-three fluoro-2-butanone (CF
3CClFCH
2C (=O) CH
3), the unknown material of about 2.5 weight % and respectively less than TFE, ethyl-methyl ether and the methyl acetate of 1 weight %.
In another particular, composition wherein of the present invention comprises acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), at least a be the solvent and the additional compound of DMF and pyridine mixtures in the case, described additional compound comprises HFO-1123, HFO-1234yf, water, formaldehyde, HCFC-124, CFC-114a, methyl acetate, methyl-formiate, 3-chloro-3,4,4,4-tetrafluoro-2-butanone, acetate 2,3,3,3-tetrafluoro propyl ester, 2-chloro-2,3,3,3-C3-Fluoroalcohol, diacetyl oxide and acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters.The additional compound typical content of this embodiment is HCFC-124 and the acetate 2-chloro-2,3,3 of about respectively 6 weight % to 8 weight %, 3-tetrafluoro propoxy-methyl esters; Water, CFC-114a, the 3-chloro-3,4,4 of about respectively 1 weight % to 4 weight %, 4-tetrafluoro-2-butanone, 2-chloro-2,3,3,3-C3-Fluoroalcohol and diacetyl oxide; And less than the resistates of about 1 weight %.
In another particular, composition wherein of the present invention comprises acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), at least a be the solvent and the additional compound of DMF and pyridine, described additional compound comprises HCFC-124, CFC-114a, methyl acetate, ethyl formate, methyl-formiate, acetate, 3-chloro-3,4,4,4-tetrafluoro-2-butanone, 2-chloro-2,3,3,3-C3-Fluoroalcohol, diacetyl oxide and acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters.The additional compound typical content of this embodiment is the acetate 2-chloro-2,3,3 of about 7 weight % to 8 weight %, 3-tetrafluoro propoxy-methyl esters; The HCFC-124 of about 3 weight %; With its excess less than about 2 weight %.
In another embodiment, comprise CF
3CClFCH
2The composition of OZnCl and at least a solvent also can comprise at least a additional compound, and described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methyl alcohol, methyl acetate, methyl-formiate, N,N-DIMETHYLACETAMIDE, dimethyl formamide, pyridine, ethyl acetate, acetate, ether, formaldehyde, trifluoro acetaldehyde, CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3, acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters (CF
3CFClCH
2OCH
2OC (=O) CH
3) and their mixture (meaning the mixture of listed any above-mentioned additional compound in this section).The described composition of the present invention of this section is called as composition D (1) hereinafter.Noticing equally, is not that all compounds of herein listing all are shown among Fig. 1.It is believed that these compounds are rendered as the impurity in impurities in raw materials, the solvent or are being used to prepare CF
3CClFCH
2The reaction conditions of OZnCl reacts any in these type dopant that form other compound down.
In a particular, comprise (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) and the composition of at least a solvent of forming by pyridine also comprise 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), methyl-formiate, methyl alcohol and trifluoro-ethylene (HFO-1123) are as additional compound.In this embodiment, described solvent is a pyridine.In this particular, described composition comprises about 80 weight % or more solvent (for pyridine), about 12 weight % or more (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl), about 3 weight % are HCFC-124 and about 1 weight % or remaining ingredient still less, and those remaining ingredients are methyl-formiate, methyl alcohol and HFO-1123.
In another particular, comprise (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) and the composition of at least a solvent of forming by DMF and pyridine mixtures also comprise tetrafluoroethylene, acetate, methyl-formiate, methyl acetate, HCFC-124, HFO-1234yf and acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3) as additional compound.In this particular, HCFC-124, CF
3CClFCH
2OC (=O) CH
3With the content of HFO-1234yf with respect to CF
3CClFCH
2OZnCl is respectively about 3 weight % to 5 weight %.
In another particular, comprise (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) and the composition of at least a solvent of forming by DMF and pyridine mixtures also comprise HFO-1123, trifluoro acetaldehyde, formaldehyde, HCFC-124, CFC-114a, methyl alcohol, methyl-formiate and acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester is an additional compound.In this embodiment, the content of HCFC-124 is with respect to (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) amount is about 13 weight % or still less, and the content of residue additional compound is 1 weight % or still less.
In another particular, comprise (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl) and the composition of at least a solvent of forming by DMF and pyridine mixtures also comprise HFO-1123, trifluoro acetaldehyde, HFO-1234yf, formaldehyde, HCFC-124, CFC-114a, methyl alcohol, dimethyl ether, methyl-formiate, ethyl formate, acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester and diacetyl oxide are as additional compound.In this embodiment, the content of HCFC-124 is about 8 weight %, and the content of other additional compound is respectively about 2 weight % or still less.
Some component of disclosed composition is commercially available acquisition, for example solvent.Other component can be made by methods known in the art.HFO-1234yf, CF
3CClFCH
2OH, CF
3CClFCH
2OZnCl and CF
3CClFCH
2OC (=O) CH
3Can as mentioned belowly make.
Composition can be made by chemical reaction hereinafter described as disclosed herein.
Chemical reaction
Before proposing following embodiment details, define or illustrate some terms earlier.As used herein, formaldehyde is meant to have H
2The compound of C=O structure, also known its can cyclic trimer 1,3,5-trioxane form exists, and can be used as Paraformaldehyde 96 or polyoxymethylene (is expressed as (H2C=O) sometimes
n).
As used herein, reactive metal is meant reactive metal, such as magnesium chips, active zinc powder, aluminium, and the powder of following any metal: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium, and zinc (II) salt.Magnesium chips is the magnesium fragment, and it is cut the small shreds to obtain to have high surface area more and generally to have a small amount of oxide on surface (it has reduced activity).The active metal powder of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium is the Rieke metal, and it is made by the special methods that can make the high surface area metal-powder, and described metal-powder is very active in reaction, such as of the present invention those.Therefore be not subjected to the constraint of any concrete theory, the Rieke metal is considered to high activity because they have high surface area and do not have the passive surface oxide compound.
As used herein, dewatering agent is gas or the gaseous mixture that comprises at least a gas, and described gas is selected from: methane, ethane, propane, butane, Sweet natural gas, alcohol, aldehyde and carbon monoxide.As used herein, Sweet natural gas is meant and contains methane as main ingredient, and comprises the gaseous mixture of a certain amount of ethane, butane, propane, carbonic acid gas, nitrogen.
As used herein, the dehydroxylation dechlorination is meant from the adjacent carbons of hydrofluoroalkane alcohol and removes a hydroxyl and chlorine atom to form HF hydrocarbon.
In one embodiment, 2-chloro-1,1,1,2-C3-Fluoroalcohol (CF
3CClFCH
2OH) can react by in reaction solvent, making CFC-114a and aldehyde and reactive metal, thereby generate 2-chloro-1,1,1,2-C3-Fluoroalcohol (CF
3CClFCH
2OH) and solvent make.So the method described in the section can make aforesaid composition B.
Alternatively, in reaction solvent, make the reaction of CFC-114a and aldehyde and reactive metal to generate metallic hydrogen fluorine alkoxide CF
3CFClCH
2The composition of OZnCl and solvent.So the method described in the section can make aforesaid composition D.
Metallic hydrogen fluorine alkoxide can be neutralized so that hydrofluoroalkane alcohol CF to be provided
3CClFCH
2OH, it can be separated.Neutralization reaction comprises uses organic solvent diluting, and with the reaction of the dilute aqueous solution of acid, include but not limited to diluted hydrochloric acid aqueous solution or dilute sulfuric acid aqueous solution.After organic solvent is isolated from aqueous phase, again with salt brine solution washing organic solvent phase.Dry then organic solvent phase, and remove solvent by evaporation or distillation, obtain hydrofluoroalkane alcohol product.
In addition, metallic hydrogen fluorine alkoxide CF
3CClFCH
2OZnCl can be used in as mentioned below other reaction, making HF hydrocarbon HFO-1234yf, and need not neutralization.So the method described in the section can make aforesaid composition A.
Except reactive metal (promptly only being zinc), also metal-salt can be joined in the mixture that comprises the CFC-114a reactant.Suitable zinc salt comprises zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate and their mixture.In one embodiment, zinc salt is a zinc acetate.The zinc salt amount that adds can be 0.1 to 1.0 mole of every mole of CFC-114a.Can be selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and isobutyric aldehyde with the aldehyde of CFC-114a reaction.The mol ratio of reactive metal and CFC-114a is about 1: 1 to about 2.5: 1.The mol ratio of aldehyde and CFC-114a is about 1: 1 to about 3: 1.
In some embodiments, wherein use Paraformaldehyde 96, quaternary ammonium salt is joined in the described reaction as aldehyde.In one embodiment, described quaternary ammonium salt is the dialkyl dimethyl ammonium acetate.Be not subjected to the constraint of any concrete theory, it is believed that this type of quaternary ammonium salt can impel Paraformaldehyde 96 to resolve into formaldehyde.In some embodiments, the amount of the quaternary ammonium salt of adding is counted about 1 weight % to about 20 weight % by the weight of Paraformaldehyde 96.In other embodiments, the amount of the quaternary ammonium salt of adding is counted about 5 weight % to about 10 weight % by the weight of Paraformaldehyde 96.
Being reflected in the reaction solvent of CFC-114a and aldehyde and reactive metal carried out.Described reaction solvent can be selected from pyridine, pyrazine or pyrimidine, alkyl nitrile and fragrant nitrile, hexamethyl-phosphoramide and their mixture of alkyl straight-chain amine or cyclammonium, dialkyl group straight chain amine or cyclammonium and trialkyl straight chain amine or cyclammonium, N-crassitude, N-methyl piperidine, sulfoxide, ether, pyridine or alkyl replacement.In another embodiment, described solvent is selected from trialkylamine, N-crassitude, N-methyl piperidine, pyridine, pyridine, dimethyl formamide, pyrazine or the pyrimidine of alkyl replacement and their mixture.In another embodiment, described reaction solvent is selected from dimethyl formamide, tetrahydrofuran (THF), pyridine, N,N-DIMETHYLACETAMIDE, 1,4-dioxane, N-Methyl pyrrolidone, ether and their mixture.In another embodiment, described solvent is the pyridine that pyridine or alkyl replace, or their mixture.In another embodiment, described solvent is selected from alcohol, ester and their mixture.In another embodiment, described solvent is selected from methyl alcohol, ethanol, methyl-formiate, methyl-sulphoxide, acetonitrile, benzonitrile and their mixture, or the mixture of these and above-mentioned any other solvent.
The water yield that exists in the reaction of CFC-114a and aldehyde and reactive metal can be less than 1000ppm.The reaction of CFC-114a and aldehyde and reactive metal can be carried out to about 100 ℃ temperature at about 30 ℃, and reaction can be implemented about 3 to about 10 hours.Before reaction, available reaction solvent is with aldehyde pre-treatment for some time.For example, with the reaction of CFC-114a and reactive metal before, make Paraformaldehyde 96 pre-treatment four hours in pyridine under 60 ℃.Pre-treatment can be carried out two to six hours, perhaps can not pre-treatment, and after joining all reactants and reaction solvent in the reaction vessel in succession, begin reaction.
The reaction of CFC-114a and aldehyde and reactive metal can be carried out in airtight container or other reactor.Described reaction can be carried out under autogenous pressure.Alternatively, the reaction of CFC-114a and aldehyde and reactive metal can be carried out in container that opens wide or reactor, and described container or reactor are equipped with suitable condenser, overflows to prevent unreacted CFC-114a.
The another kind of method of preparation HFO-1234yf comprises makes CFC-114a and aldehyde and metallic zinc reaction generate CF
3CClFCH
2OZnCl makes CF then in second step
3CClFCH
2The dechlorination of OZnCl reductibility dehydroxylation makes HFO-1234yf.
The method for preparing HFO-1234yf can comprise CF
3CClFCH
2The OZnCl neutralization is to make CF
3CClFCH
2OH; Make dewatering agent and CF
3CClFCH
2OH mixes, thereby forms gaseous mixture; And catalyzer is contacted with described gaseous mixture, thereby form HFO-1234yf.Gaseous mixture is that dewatering agent and hydrofluoroalkane alcohol are with gas phase blended mixture.
By the mixture of reaction products with mixture diluted CFC-114a, aldehyde and the reactive metal of solvent, ice and aqueous acid, described reaction product can neutralize.Described solvent can be any organic solvent of using always, such as ether.Aqueous acid can be that common mineral acid is such as aqueous solution of hydrochloric acid.After the gained mixture was stirred for some time, the layer that will comprise organic solvent was separated.With the dilute aqueous solution washing organic solvent layer of acid, then wash subsequently with salt brine solution.Dry then organic layer.By on anhydrous salt such as anhydrous magnesium sulfate or anhydrous sodium sulphate, stirring described organic layer, realize drying.Boil off organic solvent then, obtain CF
3CClFCH
2OH.
Catalyzer is at least a transition metal.Described metal is selected from: Ni, Pd and Pt.In one embodiment, described catalyzer is the loaded catalyst that comprises transition metal and carrier substance.Described carrier substance is at least a material that is selected from gac and gama-alumina.
Dewatering agent is at least a gas, and described gas is selected from: methane, ethane, propane, butane, Sweet natural gas, alcohol, aldehyde and carbon monoxide.
Mixing step carries out under the temperature between about 65 ℃ to 80 ℃ in scope.
Can be before contact procedure, with the gaseous mixture preheating.Preheating can be carried out under the temperature between about 250 ℃ to about 450 ℃ in scope.
Contact procedure is preferably carried out under the temperature between about 400 ℃ to about 700 ℃ in scope.Contact procedure was also preferably carried out about 20 to about 25 seconds.
Can neutralize then is included in remaining HF in the HFO-1234yf product, wherein by make the HFO-1234yf product come by KOH solution in and HF.Alternatively, by some other method known in the art, comprise for example component distillation, so that HF is removed from the HFO-1234yf product.
Described gaseous mixture also can comprise at least a dilution rare gas element, and described rare gas element is selected from: nitrogen, helium and argon gas.
CF
3CClFCH
2The transformation efficiency of OH to HFO-1234yf about 50% to about 100% scope.CF
3CClFCH
2The selectivity of OH to HFO-1234yf about 29% to about 100% scope.
Pressure during the contact procedure about 1 to about 100psig scope.
By in reaction solvent, making the CF that above is described as composition D
3CClFCH
2OZnCl, or above be described as the CF of composition B
3CClFCH
2OH and carboxylic acid anhydride and reactive metal reaction generate HF hydrocarbon, implement reductibility dehydroxylation dechlorination reaction.CF
3CClFCH
2OZnCl or CF
3CClFCH
2OH will generate ester CF with described anhydride reaction
3CClFCH
2OC (=O) CH
3, it is then generated HFO-1234yf by the reactive metal reduction.This 1234yf composition comprises the additional compound that above is described as composition A.
This reaction is undertaken by described, and two kinds of reagent are joined in the same reaction vessel, perhaps adds acid anhydrides separately and generates CF
3CClFCH
2OC (=O) CH
3, it can be separated.Then reactive metal is joined CF
3CClFCH
2OC (=O) CH
3In, generate HFO-1234yf.In this method, carboxylic acid anhydride is selected from diacetyl oxide, propionic anhydride, butyryl oxide, succinyl oxide, Pyroglutaric acid and adipic anhydride.Active metal powder as mentioned before.Can derive under the product mixtures situation of CFC-114a and zinc and aldehyde reaction not neutralizing, carry out reductibility dehydroxylation dechlorination reaction.Perhaps CF can isolated at first
3CClFCH
2Carry out reductibility dehydroxylation dechlorination reaction after the OH, then by generating CF with carboxylic acid anhydride and reactive metal reaction esterification
3CClFCH
2OC (=O) CH
3Any of these dehydroxylation dechlorination method all can make aforesaid composition C.
In some embodiments, reductibility dehydroxylation dechlorination reaction product is aforesaid HFO-1234yf, and it also comprises 1,3-two (trifluoromethyl)-1, and 3-difluoro tetramethylene has the tetramethylene of the replacement of following formula structure:
This compound also can be expressed from the next:
Ring-(CH
2(CF
3) CFCH
2(CF
3) CF-)-.
Carboxylic acid anhydride can be a diacetyl oxide.Acid anhydrides and CF
3CClFCH
2The mol ratio of OH is about 1: 1 to about 2: 1.Reactive metal and CF
3CClFCH
2The mol ratio of OH is about 1: 1 to about 2.5: 1.The reduction dechlorination H-H reaction can be carried out in reaction solvent, and described solvent is identical or different with the solvent of wherein CFC-114a and reactive metal and aldehyde enforcement reaction.
The chemical reaction of preparation disclosed herein composition disclosed herein especially can be used for preparing HFO-1234yf, and can not generate HFO-1234ze (1,3,3,3-tetrafluoeopropene, E-or Z-isomer).As mentioned above, this acquisition is substantially free of the product HFO-1234yf of HFO-1234ze.The gas common methods that becomes known for preparing HFO-1234yf relates to saturated compound such as 1,1,1,2,2-pentafluoropropane (HFC-245cb) and/or 1,1,1,2, the dehydrofluorination of 3-pentafluoropropane (HFC-245eb).No matter via by the use of thermal means and/or catalysis process, by whether obtaining liquid phase with causticity or vapor phase reaction, this dehydrofluorination chemical reaction all generates the HFO-1234ze of certain percentage composition.The existence of this compound is that the refrigeration agent industry is unacceptable, because it causes the performance of all types refrigeration and air-conditioning system to reduce.Therefore, must add a large amount of distillation process in any commercial production equipment rear end of adopting this chemical reaction, can from product HFO-1234yf, removing HFO-1234ze.Therefore can make any chemical reaction of the HFO-1234yf that is substantially free of HFO-1234ze, have a huge advantage industrial.
Purposes
The composition of the HFO-1234yf of comprising disclosed herein can be used as swelling agent, gaseous dielectric, fire-fighting medium and the fireproofing agent of low Global warming potentiality (GWP) heat exchange composition, aerosol propellants, foam expansion agent (also being called as whipping agent or bubbling agent), solvent, sanitising agent, carrier fluid, substituted type siccative, polishing abrasive, polymerization reaction medium, polyolefine and the urethane of liquid or gas form.Disclosed composition can be used as working fluid, is used for heat is transported to scatterer from thermal source.This type of heat transfer composition also can be used as the refrigeration agent in the circulation, wherein the phase transformation of fluid experience; Promptly become gas from liquid, and become liquid again again, perhaps vice versa.
The example of heat transfer systems includes but not limited to air-conditioning, refrigerator, reezer system, thermal pump, watercooler, full liquid type evaporative cooler, direct expansion formula water cooler, steps into formula refrigerator, thermal pump, portable reezer system, movable air conditioner device, and their combination.
In one embodiment, the composition that comprises HFO-1234yf can be used in the portable heat transfer systems, comprises in refrigeration, air-conditioning or thermal pump system or the equipment.In one embodiment, described composition can be used in the fixed heat transfer systems, comprises in refrigeration, air-conditioning or thermal pump system or the equipment.
As used herein, portable heat transfer systems is meant any refrigeration, air-conditioning or the heating installation that is incorporated in highway, railway, the sea or air conveyer.In addition, portable refrigeration or air-conditioning plant comprise those equipment that are independent of any mobile vehicle and are called as " intermodal transportation " system.This type of intermodal transportation system comprises " freight container " (sea route/land route intermodal transportation) and " but demolition loading space " (highway/railway combined haulage).
As used herein, fixed heat transfer systems is the system that is fixed on a place between on-stream period.Fixed heat transfer systems can be attached among any kind building or be attached on it, perhaps can be the stand-alone device that is positioned at outdoors, such as the soft drink vending machine.These stationary applications can be that fixed air-conditioning and thermal pump (include but not limited to water cooler, the high temperature thermal pump, dwelling house, commerce or industrial air-conditioning system, and comprise the terminal water cooler of window cooler, pipe free water cooler, catheter type water cooler, monoblock type, and at building external but be connected with building those such as the roof system).In stationary refrigeration applications, disclosed composition can be used in the equipment, described equipment comprises commerce, industry or dwelling house reezer system and refrigerator, ice-making machine, monoblock type cooler and refrigerator, full liquid type evaporative cooler, direct expansion formula water cooler, steps into formula and hand modus ponens cooler and refrigerator, and the combination of system.In some embodiments, disclosed composition can be used in the reezer system system of supermarket.
Comprise CF
3CClFCH
2OH; Can be used for preparing in the method for HFO-1234yf as mentioned above with the composition disclosed herein of at least a solvent.
Comprise CF
3CClFCH
2OC (=O) CH
3Can be used for preparing in the method for HFO-1234yf as mentioned above with the composition disclosed herein of at least a solvent.
Comprise CF
3CClFCH
2OZnCl; Can be used for preparing in the method for HFO-1234yf as mentioned above with the composition disclosed herein of at least a solvent.
It is bright to need not more to speak more, and those of skill in the art should be able to maximally utilise the present invention according to the description of this paper.Therefore, following specific embodiments is interpreted as only doing the usefulness of example, and retrains disclosure rest part never in any form.
Embodiment
Notion described herein will further describe in the following example, and described embodiment is not limited in the scope of describing in the claim of the present invention.The result who provides with GC or GC-MS area percentage mode is considered to proximate weight percent.
Embodiment 1
Embodiment 1 shows by 1,1,1,2-tetrafluoro-2,2-ethylene dichloride (CFC-114a) preparation 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH)) method, and the concrete reaction product that obtains of preparation method thus.
At N
2Down to 400mL Hastelloy
TMIn the C oscillion, add 32.8 gram (0.5 mole) active zinc powders, 12 gram (0.5 mole) Paraformaldehyde 96 and 180mL anhydrous dimethyl formamides (DMF).Described pipe is cooled to-15 ℃, and adds 64.4 gram (0.2 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a).Under 50 ℃, reaction mixture was stirred 6 hours then.The gas chromatographic analysis of reaction product the results are summarized in the table 1.Reaction mixture is cooled to room temperature, is poured into then in the 200mL mixture of ice, the 10%HCl aqueous solution and 200mL ether.With described solution stirring 30min, and isolate organic layer, and, use the water washing of 100mL salt then with the HCl solution washing of 100mL 2%.Use MgSO
4Dry organic layer, and vacuum removes ether, acquisition 13.36 gram product 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), thus obtain 8% yield.
Table 1
| Component | GC area percentage (%) |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 7.076 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 8.18 |
| Methyl alcohol | 0.335 |
| DMF | 83.9 |
Embodiment 2
Embodiment 2 shows by 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a) Synthetic 2,3,3, the method for 3-tetrafluoeopropene, and the concrete reaction product that obtains of synthetic method thus.
At N
2Down to 400mL Hastelloy
TMIn the C oscillion, add 20 gram (0.315 mole) active zinc powders, 7.5 gram (0.25 mole) Paraformaldehyde 96 and 130mL dry DMF.Described pipe is cooled to-15 ℃, and adds 43 gram (0.25 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a).Reaction mixture was stirred 6 hours down at 60 ℃, be cooled to room temperature then.In reactor, add 30 gram (0.46 mole) active zinc powders and 50 gram (0.5 mole) diacetyl oxides.Under 50 ℃, reaction mixture was stirred 6 hours, be cooled to room temperature then.Analyze gas phase and liquid phase by gas chromatography-mass spectrography analyser (GC-MS).The results are summarized in the table 2.The 1234yf composition is shown in the gas phase part of following table 2, and the liquid phase part of table 2 is to stay in reactor those after gas sample leaves.Notice that the gas phase sample is corresponding to the composition that comprises HFO-1234yf and additional compound.
Table 2
| Component (staying the liquid phase in the reactor after the reaction) | GC area percentage (%) |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 5.50 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 16.93 |
| 3,4,4,4-tetrafluoro-2-butanone | 3.7 |
| Acetylfluoride | 4.57 |
| Methyl acetate | 4.72 |
| Acetate | 52.7 |
| Diacetyl oxide | 4.88 |
| Component (gas phase HFO-1234yf product) | GC area percentage (%) |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 83.42 |
| Tetrafluoroethylene | 0.75 |
| Vinylidene fluoride | 0.28 |
| Trifluoro-ethylene | 1.69 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 11.62 |
Embodiment 3
Embodiment 3 shows the pyridine solution Synthetic 2-chloro-2,3,3 by CFC-114a, 3-C3-Fluoroalcohol (CF
3CClFCH
2OH) method, and the concrete reaction product that obtains of synthetic method thus.
At N
2In 80mL Fisher Porter pipe, add 2.24 gram (0.034 mole) active zinc powders, 1.24 gram (0.041 mole) Paraformaldehyde 96 and 30mL anhydrous pyridines down.Pipe is cooled to-15 ℃, and adds 5 gram (0.029 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a), and reaction mixture stirred 8 hours down at 50 ℃.When reaction finished, reactor pressure was reduced to 8psig from 25psig.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.Data are reported in the table 3 with the GC-MS area percentage.
Table 3
(liquid phase)
| Component | GC-MS area percentage (%) |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 8.586 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 2.887 |
| Methyl-formiate | 0.420 |
| Trifluorochloroethylene (CFO-1113) | 0.637 |
| Trifluoro-ethylene (HFO-1123) | 0.0140 |
| Methyl alcohol | 0.135 |
| Pyridine | 87.194 |
Embodiment 4
Embodiment 4 shows 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) synthetic method of dimethylacetamide solution, and the concrete reaction product that obtains of synthetic method thus.
At N
2In 80mL Fisher Porter pipe, add 2.23 gram (0.034 mole) active zinc powders, 1.21 gram (0.040 mole) Paraformaldehyde 96 and 30mL anhydrous dimethyl yl acetamides down.Described pipe is cooled to-15 ℃, and adds 5.2 gram (0.030 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a).Reaction mixture was stirred 4.5 hours down at 60 ℃.When reaction finished, reactor pressure was reduced to 9psig from 30psig.Reaction mixture is cooled to room temperature, and it is analyzed by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.Data are reported in the table 4 with the GC-MS area percentage.
Table 4
(liquid phase)
| Component | GC-MS area percentage (%) |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 5.750 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 2.181 |
| Methyl-formiate | 0.181 |
| Trifluorochloroethylene (CFO-1113) | 2.634 |
| Trifluoro-ethylene (HFO-1123) | 0.029 |
| N,N-DIMETHYLACETAMIDE | 88.463 |
Embodiment 5
Embodiment 5 shows under pre-treatment formaldehyde situation, CF
3CClFCH
2The synthetic method of OZnCl pyridine solution, and the concrete reaction product that obtains of synthetic method thus.
At N
2In 80mL Fisher Porter pipe, add 1.82 gram (0.06 mole) Paraformaldehyde 96 and 30mL anhydrous pyridines down.Pipe is heated to 60 ℃, and stirred 4 hours.Pipe is cooled to room temperature, and adds 2.24 gram (0.034 mole) activated zinc powder.Using N
2Purge after 15 minutes, pipe is cooled to-15 ℃, and add 5 gram (0.029 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a).Then reaction mixture was stirred 8 hours down at 50 ℃.When reaction finished, reactor pressure was reduced to 9psig from 25psig.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.Data are reported in the table 5 by the area percentage of GC-MS.114a is to CF
3CClFCH
2The selectivity of OZnCl (is pressed CF
3CClFCH
2OH analyzes) increase to 78.7%.
Table 5 (liquid phase)
Embodiment 6
Embodiment 6 shows with diacetyl oxide esterification 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) make CF
3CClFCH
2OC (=O) CH
3Reaction, and the reaction product that obtains of esterification thus.
In 80mL Fisher Porter pipe, add 2 gram (0.012 mole) CF
3CClFCH
2OH (it comprises about 15% ether), 1.35 gram (0.0132 mole) diacetyl oxides and the 0.25 gram vitriol oil.Mixture was stirred 6 hours down at 60 ℃.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in the table 6 by the area percentage of GC-MS.These results show, the CF greater than 99%
3CClFCH
2OH has been converted into CF
3CClFCH
2OC (=O) CH
3
Table 6
| Component | GC-MS area percentage (%) |
| Acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF 3CClFCH 2OC(＝O)CH 3) | 72.55 |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 0.198 |
| Ethyl acetate | 3.12 |
| Acetate | 17.24 |
| Ether | 6.19 |
Embodiment 7
Embodiment 7 shows CF
3CClFCH
2OZnCl to CF
3CClFCH
2OC (=O) CH
3Direct esterification reaction, and the reaction product that obtains of direct esterification reaction thus.
At room temperature vacuum distilling 10mL comprises about 14%CF
3CClFCH
2The pyridine solution of OZnCl is to remove most of pyridine.Then 2.0 gram diacetyl oxides and 1mL DMF are joined in the gained solid.Mixture was stirred 7 hours down at 60 ℃.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in the table 7 with the GC-MS area percentage.
Table 7
| Component | GC-MS area percentage (%) |
| Acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF 3CClFCH 2OC(＝O)CH 3) | 71.8 |
| Formic acid 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF 3CClFCH 2OCH(＝O)) | 2.01 |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 0.115 |
| Diacetyl oxide | 2.61 |
| Acetate | 2.58 |
| DMF/ pyridine (solvent) | 13.22 |
Embodiment 8
Embodiment 8 shows acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3) to 2,3,3, the conversion of 3-tetrafluoeopropene (HFO-1234yf).
Above reaction mixture and the 1 gram Na of embodiment 7 will be derived from
2CO
3Stir together, to remove the acid that generates in the esterif iotacation step.Add 3 moles of DMF and 1.3 gram Zn then.In 80mL Fisher Porter pipe, make to be reflected under stirring and carried out under 50 ℃ 2 hours, and under 60 ℃, carried out again 2 hours.Reactor pressure rises to 13psig from 0psig.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in the table 8 by the area percentage of GC-MS.CF in the reactor liquid phase
3CClFCH
2OC (=O) CH
3Become and to detect.This result shows, under these conditions CF
3CClFCH
2OC (=O) CH
3Quantitative yield becomes 2,3,3,3-tetrafluoeopropene (HFO-1234yf).Notice that the vapor phase sample is corresponding to the composition that comprises HFO-1234yf and additional compound.
Table 8
| Component (vapor phase) | GC-MS area percentage (%) |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 94.48 |
| 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF 3CClFCH 2OH) | 0.115 |
| Diacetyl oxide | 1.62 |
| Methyl acetate | 0.815 |
| DMF | 1.05 |
| Pyridine | 2.05 |
| (liquid phase) | |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 1.61 |
| Diacetyl oxide | 1.45 |
| Methyl acetate | 0.61 |
| DMF | 86.24 |
| Pyridine | 9.98 |
Embodiment 9
Embodiment 9 illustrates, in dimethyl formamide and pyridine mixed solvent, and 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a) generates (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF with polyformaldehyde reaction
3CClFCH
2OZnCl).
At N
2In 80mL Fisher Porter pipe, add 2.2 gram Zn (0.037 mole), 0.3 gram zinc acetate (0.0016 mole), 2 gram (0.067 mole) Paraformaldehyde 96s, 15 gram anhydrous pyridines and 15 gram dimethyl formamides down.At N
2Purge after 15 minutes, pipe is cooled to-15 ℃, and add 5 gram (0.029 moles) 1,1-two chloro-1,2,2,2-Tetrafluoroethane (CFC-114a), and reaction mixture stirred 2 hours down at 50 ℃.When reaction finished, reactor pressure was reduced to 5psig from 25psig.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.Data are reported in (DMF and pyridine peak are got rid of outside integration, promptly are present in the sample) in the table 9 with the area percentage that derives from GC-MS.Analyze CFC-114a to CF based on GC-MS
3CClFCH
2OZnCl (as 2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH) analyze) selectivity be 83%.
Table 9 (liquid phase)
Embodiment 10
Embodiment 10 is illustrated in the solvent mixture with diacetyl oxide CF
3CClFCH
2The OZnCl direct esterification becomes CF
3CClFCH
2OC (=O) CH
3Reaction and the reaction product that obtains of esterification thus.
The excessive Zn of elimination from the reaction mixture that derives from embodiment 9 joins filtrate in the 80mL Fisher Porter pipe then, and adds 4.4 gram diacetyl oxides (0.043 mole).Mixture was stirred 6 hours down at 60 ℃.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in (DMF, pyridine and diacetyl oxide are got rid of outside integration) in the table 10 with the area percentage of GC-MS, and promptly they are present in the final composition.This result shows, under these reaction conditionss, and the CF greater than 94%
3CClFCH
2OZnCl has changed into CF
3CClFCH
2OC (=O) CH
3
Table 10 (liquid phase)
| Component | The GC-MS area percentage |
| TFE | 0.477 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 5.97 |
| 3-chloro-3,4,4,4-three fluoro-2-butanone (CF 3CClFCH 2C(＝O)CH 3) | 2.57 |
| Ethyl-methyl ether | 0.83 |
| Methyl acetate | 0.92 |
| Acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF 3CClFCH 2OC(＝O)CH 3) | 85.3 |
| Unknown material | 2.46 |
Embodiment 11
Embodiment 11 shows the pyridine at 3: 1: in the DMF solvent by 1,1,1,2-tetrafluoro-2,2-ethylene dichloride (CFC-114a) Synthetic 2,3,3, the method for 3-tetrafluoeopropene (HFO-1234yf).
At N
2In 80mL Fisher Porter pipe, add 2.1 gram Metal Zn (0.032 mole), 0.3 gram zinc acetate (0.0016 mole), 2 gram (0.067 mole) Paraformaldehyde 96s, 30 gram anhydrous pyridines down.Using N
2Purge after 15 minutes, pipe is cooled to-15 ℃, and add 5 gram (0.029 moles) 1,1-dichloro tetrafluoro ethane (CFC-114a).Under 50 ℃, reaction mixture was stirred 3 hours then.When reaction finished, reactor pressure was reduced to 5.5psig from 25psig.After reaction mixture is cooled to room temperature, it is analyzed by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.Solvent (pyridine) peak is got rid of outside integration.Data are reported in the table 11 with the GC-MS area percentage.Analyze based on GC-MS, 1, the 1-dichloro tetrafluoro ethane is to CF
3CClFCH
2OZnCl is (as CF
3CClFCH
2OH analyzes) selectivity be 81%.
The excessive zinc of filtering from reaction mixture, and it is joined in the 80mL Fisher Porter pipe.Also 10mL dry DMF and 3.5 gram diacetyl oxides (0.034 mole) are joined in the described reactor.Mixture was stirred 4 hours down at 60 ℃.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in the table 12 with the GC-MS area percentage.Solvent (DMF and pyridine) peak is got rid of outside integration.This result shows, the CF greater than 98%
3CClFCH
2OZnCl is transformed, and to CF
3CClFCH
2OC (=O) CH
3And CF
3CFClCH
2OCH
2OC (=O) CH
3Selectivity be 89%.
The above-mentioned reaction mixture of 10mL is stayed in the 80mL Fisher Porter pipe, and added active zinc powder (1 gram, 0.015 mole).Make to be reflected under stirring and carried out under 60 ℃ 4 hours.Reactor pressure rises to 15.5psig from 6psig.Reaction mixture is cooled to room temperature, and analyzes vapor phase and liquid phase by GC-MS.Data are reported with the GC-MS area percentage.Vapor phase (product 2,3,3,3-tetrafluoeopropene) data are listed in the table 13, and liquid phase (the reaction back is residual) data are listed in (DMF and pyridine solvent peak are got rid of outside integration) in the table 14.CF
3CClFCH
2OC (=O) CH
3In the reactor liquid phase, become and to detect.Analysis revealed, to 2,3,3, the selectivity of 3-tetrafluoro-1-propylene (HFO-1234yf) is about 94%, and to 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C
6H
4F
8) selectivity be about 5%.
Table 11
Liquid phase CF
3
CClFCH
2
OZnCl is (as CF
3
CClFCH
2
OH analyzes)
Table 12
Liquid phase 2-chloro-2,3,3, the 3-C3-Fluoroalcohol
Table 13
Vapor phase product (2,3,3, the 3-tetrafluoeopropene)
| Compound | GC-MS area percentage (%) |
| Tetrafluoroethylene (TFE) | 0.08 |
| Trifluoro-ethylene (HFO-1123) | 5.84 |
| 1,1, the 1-Halothane | 0.02 |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 79.93 |
| Trifluorochloroethylene (CFO-1113) | 0.06 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 9.10 |
| 1,1-two chloro-1,2,2,2-Tetrafluoroethane | 0.05 |
| 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C 6H 4F 8) | 4.00 |
| Methyl-formiate | 0.04 |
| Acetate | 0.19 |
| Acetate 2,3,3,3-tetrafluoro propyl ester | 0.1 |
| Unknown material | 0.85 |
Table 14
Liquid phase (the reaction back is residual)
| Compound | GC-MS area percentage (%) |
| Trifluoro-ethylene (HFO-1123) | 0.98 |
| 1,1,1-Halothane (HFC-143a) | 0.49 |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 36.85 |
| Water | 8.26 |
| Methyl alcohol | 0.25 |
| Acetate | 3.47 |
| 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) | 20.45 |
| Methyl acetate | 2.10 |
| Methyl-formiate | 0.32 |
| 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C 6H 4F 8) | 7.91 |
| Acetate 2,3,3-three fluoro-2-propylene-1-esters | 2.02 |
| Acetate 2,3,3,3-tetrafluoro propyl ester | 2.92 |
| Methyl ethyl ether | 1.462 |
| Diacetyl oxide | 7.245 |
| Unknown material | 5.27 |
Embodiment 12
Embodiment 12 shows the pyridine at 1: 1: in the DMF solvent by 1,1,1,2-tetrafluoro-2,2-ethylene dichloride (CFC-114a) Synthetic 2,3,3, the method for 3-tetrafluoeopropene (HFO-1234yf).
At N
2In 80mL Fisher Porter pipe, add 2.1 gram metallic zinc (0.032 mole), 0.3 gram zinc acetate (0.0016 mole), 2 gram (0.067 mole) Paraformaldehyde 96s, 0.2 gram two (hydrogenation alkyl) dimethyl acetic acid ammoniums and 30 gram anhydrous pyridines down.Using N
2Purge after 15 minutes, pipe is cooled to-15 ℃, and add 5 gram (0.029 moles) 1,1-dichloro tetrafluoro ethane (CFC-114a).Then reaction mixture was stirred 3 hours down at 50 ℃.When reaction finished, reactor pressure was reduced to 5.5psig from 23psig.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Analyze for carrying out GC-MS, with the acetone soln acidifying part reaction mixture of 10%HCl.DMF and pyridine solvent are got rid of outside integration.Data are reported in the table 15 with the area percentage that derives from the GC-MS data.Analyze CFC-114a to CF based on GC-MS
3CClFCH
2OZnCl is (as CF
3CClFCH
2OH analyzes) selectivity be about 85%.
Filter the 10mL reaction mixture, and join in the 80mL Fisher Porter pipe.Also 10mL dry DMF and 3.5 gram diacetyl oxides (0.034 mole) are joined in the described reactor.Mixture was stirred 4 hours down at 60 ℃.Reaction mixture is cooled to room temperature, and analyzes by GC-MS.Data are reported in the table 16 with the area percentage that derives from the GC-MS data.DMF and pyridine solvent peak are got rid of outside integration.This result shows, the CF greater than 98%
3CClFCH
2OZnCl is transformed, and CF
3CClFCH
2OC (=O) CH
3And CF
3CFClCH
2OCH
2OC (=O) CH
3Selectivity be about 95%.
In 80mL Fisher Porter pipe, with 2 gram Na
2CO
3Reaction mixture.At elimination Na
2CO
3After, add active zinc powder (1 gram, 0.015 mole).In 80mL Fisher Porter pipe, make under stirring to be reflected at 60 ℃ and to carry out 4 hours.Reactor pressure rises to 18psig from 5psig.Reaction mixture is cooled to room temperature, and analyzes liquid phase and vapor phase by GC-MS.Data are reported with the GC-MS area percentage.The results are shown in Table 17 for vapor phase (product 2,3,3,3-tetrafluoeopropene), and liquid phase (the reaction back is residual) result is reported in (DMF and pyridine solvent peak are got rid of outside integration) in the table 18.CF greater than 99%
3CClFCH
2OC (=O) CH
3With greater than 95% CF
3CFClCH
2OCH
2OC (=O) CH
3Transformed.Analysis revealed, the selectivity of HFO-1234yf are about 98%, and 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C
6H
4F
8) selectivity be about 0.1%.
Table 15
Liquid phase CF
3
CClFCH
2
OZnCl is (as CF
3
CClFCH
2
OH divides newly)
Table 16
Liquid phase acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester
Table 17
Vapor phase product (2,3,3, the 3-tetrafluoeopropene)
| Compound | GC-MS area percentage (%) |
| Trifluoro-ethylene (HFO-1123) | 0.72 |
| 2,3,3,3-tetrafluoeopropene (HFO-1234yf) | 97.46 |
| Water | 0.04 |
| Trifluorochloroethylene (CFO-1113) | 0.06 |
| 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C 6H 4F 8) | 0.1 |
| Methyl-formiate | 0.08 |
| Methyl acetate | 0.1 |
| Unknown material | 0.1 |
Table 18
Liquid phase (the reaction back is residual)
Notice, above general describe or embodiment described in behavior not all is necessary, a part of concrete behavior is optional, and those, also can implement one or more other behaviors except described.In addition, the order of listed behavior needs not to be the order of implementing them.
In above-mentioned specification sheets, with reference to specific embodiment different concepts has been described.Yet those of ordinary skill in the art recognizes, under the situation that does not break away from the scope of the invention as hereinafter described in the claims, can carry out various modifications and variations.Therefore, it is exemplary and nonrestrictive that specification sheets and accompanying drawing should be considered to, and all these type of modification all are intended to be included in the scope of the present invention.
The solution of beneficial effect, other advantages and problem has above been described in conjunction with specific embodiment.Yet, the solution of beneficial effect, advantage, problem and can cause any beneficial effect, advantage or solution produces or the more significant any feature that becomes may not be interpreted as the key of any or all claim, essential or essential characteristic.
Will be appreciated that for clarity sake, some characteristic described in the context of this paper different embodiments also can provide with array mode in single embodiment.Otherwise for simplicity, a plurality of characteristics described in single embodiment context also can provide respectively, or provide in the mode of any sub-portfolio.In addition, the correlation values of describing in the scope comprises each value in the described scope.
As used herein, term " comprises ", " comprising ", " having " or their any other modification all are intended to contain comprising of nonexcludability.For example, comprise that technology, method, goods or the equipment of key element tabulation needn't only limit to those key elements, but can comprise clearly do not list or this technology, method, goods or equipment institute other key elements of inherent.In addition, unless opposite offering some clarification on arranged, " or " be meant inclusive " or ", rather than refer to exclusiveness " or ".For example, below all satisfy condition A or B:A of any situation be that real (or existence) and B are false (or non-existent), A is that false (or non-existent) and B are real (or existence), and A and B are real (or existence).
Equally, use " one " or " a kind of " to describe key element described herein and component.Doing so only is for convenience, and provides general meaning to scope of the present invention.This description should be understood to include one or at least one, and this odd number also comprises plural number, anticipates unless clearly refer to him in addition.
Unless otherwise defined, equal the same with those skilled in the art's common sense of the implication of all technology used herein and scientific terminology.Although also can be used for hereinafter having described suitable method and material in the enforcement or test of embodiment of the present invention with method described herein and materials similar or the method that is equal to and material.Remove the non-quoted physical segment and fall, otherwise all publications that this paper mentions, patent application, patent and other reference all in full way of reference incorporate this paper into.As conflict, the definition included with this specification sheets is as the criterion.In addition, material, method and embodiment only are exemplary, are not intended to limit.
Claims (27)
1. the composition that comprises HFO-1234yf and at least a additional compound, described additional compound are selected from CFC-114a (2-two chloro-1,1,1,2-Tetrafluoroethane, CCl
2FCF
3), HCFC-124 (2-chloro-1,1,1,2-Tetrafluoroethane, CF
3CHFCl), HFC-143a (1,1,1-Halothane, CF
3CH
3), CFO-1113 (2-chloro-1,1,2-trifluoro-ethylene, CClF=CF
2), HFO-1123 (1,1,2-trifluoro-ethylene, CHF=CF
2), HFO-1132a (vinylidene fluoride, CH
2=CF
2), TFE (tetrafluoroethylene, CF
2=CF
2), HCFO-1122 (2-chloro-vinylidene fluoride, CHCl=CF
2), 3,4,4,4-tetrafluoro-2-butanone (CH
3C (=O) CHFCF
3), acetylfluoride (CH
3C (=O) F), 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3), (2-chloro-2,3,3,3-tetrafluoro propoxy-) zinc chloride (CF
3CClFCH
2OZnCl), acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters (CF
3CFClCH
2OCH
2OC (=O) CH
3), 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene (C
6H
4F
8), acetate 2,3,3,3-tetrafluoro propyl ester (CF
3CHFCH
2OC (=O) CH
3), dimethyl formamide (DMF, HCON (CH
3)
2), pyridine (C
5H
5N), ethyl acetate, (CHClFCF
3), acetate (CH
3C (=O) OH), ether (CH
3CH
2OCH
2CH
3), diacetyl oxide (CH
3C (=O) OC (=O) CH
3), methyl acetate (CH
3C (=O) OCH
3), N,N-DIMETHYLACETAMIDE (CH
3C (=O) N (CH
3)
2), methyl alcohol (CH
3OH), ethanol (CH3CH2OH), methyl-formiate (HC (=O) OCH
3), pyrazine, pyrimidine, N-crassitude, N-methyl piperidine, hexamethyl-phosphoramide, tetrahydrofuran (THF), 1,4-dioxane, N-Methyl pyrrolidone, methyl-sulphoxide, acetonitrile, benzonitrile and their mixture.
2. the composition of claim 1, wherein said additional compound comprises tetrafluoroethylene, 1,1, difluoroethylene, trifluoro-ethylene and 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124).
3. the composition of claim 1, wherein said additional compound comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), diacetyl oxide, methyl acetate, DMF and pyridine.
4. the composition of claim 1, wherein said additional compound comprises TFE, HFO-1123, HFC-143a, CFO-1113, HCFC-124, CFC-114a, 1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene, methyl-formiate, acetate and acetate 2,3,3,3-tetrafluoro propyl ester.
5. the composition of claim 1, wherein said additional compound comprises HFO-1123, water, CFO-1113,1,3-two (trifluoromethyl)-1,3-difluoro tetramethylene, methyl-formiate and methyl acetate.
6. composition, it comprises:
A.CF
3CClFCH
2OH; With
B. at least a solvent.
7. the composition of claim 6, described composition also comprises at least a additional compound, and described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, N,N-DIMETHYLACETAMIDE, methyl alcohol, methyl acetate, methyl-formiate, DMF, pyridine, ethyl acetate, acetate, ether, CF
3CClFCH
2OZnCl, CF
3CClFCH
2OC (=O) CH
3, acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters and their mixture.
8. the composition of claim 7, wherein said additional compound comprises HCFC-124 and methyl alcohol.
9. the composition of claim 7, wherein said additional compound comprises 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), methyl-formiate, trifluorochloroethylene (CFO-1113), trifluoro-ethylene (HFO-1123) and methyl alcohol.
10. the composition of claim 7, wherein said additional compound comprises 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), methyl-formiate, trifluorochloroethylene (CFO-1113) and trifluoro-ethylene (HFO-1123).
11. composition, it comprises:
A.CF
3CClFCH
2OC (=O) CH
3With
B. at least a solvent.
12. the composition of claim 11, described composition also comprises at least a additional compound, described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methyl alcohol, methyl acetate, methyl-formiate, N,N-DIMETHYLACETAMIDE, dimethyl formamide, pyridine, ethyl acetate, acetate, ether, diacetyl oxide, formaldehyde, 3-chloro-3,4,4,4-three fluoro-2-butanone, acetate 2,3,3,3-tetrafluoro propyl ester, CF
3CClFCH
2OCH (=O), acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters, CF
3CClFCH
2OH, CF
3CClFCH
2OZnCl and their mixture.
13. the composition of claim 12, wherein said additional compound comprises 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), ethyl acetate, acetate and ether.
14. the composition of claim 12, wherein said additional compound comprise formic acid 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OCH (=O)), 2-chloro-2,3,3,3-C3-Fluoroalcohol (CF
3CClFCH
2OH), diacetyl oxide and acetate.
15. the composition of claim 12, wherein said additional compound comprise TFE, HCFC-124,3-chloro-3,4,4,4-three fluoro-2-butanone, ethyl-methyl ether and methyl acetate.
16. the composition of claim 12, wherein said additional compound comprise HFO-1123, HFO-1234yf, water, formaldehyde, HCFC-124, CFC-114a, methyl acetate, methyl-formiate, 3-chloro-3,4,4,4-tetrafluoro-2-butanone, acetate 2,3,3,3-tetrafluoro propyl ester, 2-chloro-2,3,3,3-C3-Fluoroalcohol, diacetyl oxide and acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters.
17. the composition of claim 12, wherein said additional compound comprises HCFC-124, CFC-114a, methyl acetate, ethyl formate, methyl-formiate, acetate, 3-chloro-3,4,4,4-tetrafluoro-2-butanone, 2-chloro-2,3,3,3-C3-Fluoroalcohol, diacetyl oxide and acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters.
18. composition, it comprises:
A.CF
3CClFCH
2OZnCl; With
B. at least a solvent.
19. the composition of claim 18, described composition also comprises at least a additional compound, and described additional compound is selected from HFO-1234yf, CFC-114a, HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methyl alcohol, methyl acetate, methyl-formiate, N,N-DIMETHYLACETAMIDE, dimethyl formamide, pyridine, ethyl acetate, acetate, ether, formaldehyde, trifluoro acetaldehyde, CF
3CClFCH
2OH, CF
3CClFCH
2OC (=O) CH
3, acetate 2-chloro-2,3,3,3-tetrafluoro propoxy-methyl esters (CF
3CFClCH
2OCH
2OC (=O) CH
3) and their mixture.
20. the composition of claim 19, wherein said additional compound comprises HCFC-124, methyl-formiate, methyl alcohol and HFO-1123.
21. the composition of claim 19, wherein said additional compound comprise TFE, acetate, methyl-formiate, methyl acetate, HCFC-124, HFO-1234yf and acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester (CF
3CClFCH
2OC (=O) CH
3).
22. the composition of claim 19, wherein said additional compound comprise HFO-1123, trifluoro acetaldehyde, formaldehyde, HCFC-124, CFC-114a, methyl alcohol, methyl-formiate and acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester.
23. the composition of claim 19, wherein said additional compound comprises HFO-1123, trifluoro acetaldehyde, HFO-1234yf, formaldehyde, HCFC-124, CFC-114a, methyl alcohol, dimethyl ether, methyl-formiate, ethyl formate, acetate 2-chloro-2,3,3,3-tetrafluoro propyl ester and diacetyl oxide.
24. the composition of claim 1, described composition comprise greater than 0 weight % to the described at least a additional compound less than 1 weight %.
25. claim 6,11 or 18 composition, wherein said solvent is selected from alkyl straight streptamine or cyclammonium, dialkyl group straight chain amine or cyclammonium or trialkyl straight chain amine or cyclammonium; Pyridine, pyrazine, pyrimidine that pyridine or alkyl replace; Sulfoxide, ether, alkyl nitrile or fragrant nitrile, hexamethyl-phosphoramide; Alcohol; Ester, dimethyl formamide, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, 1,4-dioxane and N-Methyl pyrrolidone and their mixture.
26. the composition of claim 25, wherein said solvent are selected from methyl alcohol, ethanol, methyl-formiate, DMSO, acetonitrile, benzonitrile and their mixture.
27. the composition of claim 25, wherein said solvent are selected from N,N-DIMETHYLACETAMIDE, dimethyl formamide, pyridine and their mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10433408P | 2008-10-10 | 2008-10-10 | |
| US61/104334 | 2008-10-10 | ||
| PCT/US2009/060094 WO2010042781A2 (en) | 2008-10-10 | 2009-10-09 | Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride |
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|---|---|
| CN102177118A true CN102177118A (en) | 2011-09-07 |
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|---|---|---|---|
| CN2009801401143A Pending CN102177118A (en) | 2008-10-10 | 2009-10-09 | Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride |
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| US (2) | US8147710B2 (en) |
| EP (1) | EP2331489A2 (en) |
| JP (1) | JP2012505296A (en) |
| KR (1) | KR20110084910A (en) |
| CN (1) | CN102177118A (en) |
| AU (1) | AU2009302263A1 (en) |
| BR (1) | BRPI0913806A2 (en) |
| CA (1) | CA2736216A1 (en) |
| MX (1) | MX2011003633A (en) |
| RU (1) | RU2011118429A (en) |
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- 2009-10-09 KR KR1020117010557A patent/KR20110084910A/en not_active Withdrawn
- 2009-10-09 US US12/576,388 patent/US8147710B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2736216A1 (en) | 2010-04-15 |
| US8147710B2 (en) | 2012-04-03 |
| US20100090156A1 (en) | 2010-04-15 |
| EP2331489A2 (en) | 2011-06-15 |
| TW201022425A (en) | 2010-06-16 |
| RU2011118429A (en) | 2012-11-20 |
| AU2009302263A1 (en) | 2010-04-15 |
| KR20110084910A (en) | 2011-07-26 |
| WO2010042781A3 (en) | 2010-07-08 |
| WO2010042781A2 (en) | 2010-04-15 |
| MX2011003633A (en) | 2011-05-02 |
| JP2012505296A (en) | 2012-03-01 |
| US8518294B2 (en) | 2013-08-27 |
| BRPI0913806A2 (en) | 2015-10-20 |
| US20120168672A1 (en) | 2012-07-05 |
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